The present invention relates to oil-soluble copolymers of ethylene and further comonomers which contain one or more hydroxyl groups, and their use for improving the lubricity of fuel oils.
Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5% by weight or more of sulfur, which, on burning, causes the formation of sulfur dioxide. In order to reduce the resultant environmental pollution, the sulfur content of fuel oils is continually being reduced further. The EN 590 standard relating to diesel fuels currently prescribes a maximum sulfur content of 500 ppm in Germany. In Scandinavia, fuel oils containing less than 200 ppm and in exceptional cases less than 50 ppm of sulfur are already in use. These fuel oils are generally produced by hydrotreating the fractions obtained from the crude oil by distillation. However, the desulfurization also removes other substances which provide the fuel oils with a natural lubricating action. These substances include, inter alia, polyaromatic and polar compounds.
However, it has now been found that the friction- and wear-reducing properties of fuel oils worsen with increasing degree of desulfurization. These properties are frequently so poor that the fuel-lubricated materials, such as, for example, the distributor injection pumps of diesel engines, can be expected to exhibit signs of wear after only a short time. The further lowering of the 95% distillation point to below 370xc2x0 C., in some cases to below 350xc2x0 C. or 330xc2x0 C., which has in the meantime been carried out in Scandinavia, further exacerbates this problem.
The prior art therefore describes attempts to solve this problem (so-called lubricity additives).
EP-A-0 680 506 discloses esters of carboxylic acids having 2 to 50 carbon atoms as additives for improving the lubricating action of low-sulfur middle distillates containing less than 0.5% by weight of S.
DD-126 090 discloses lubricity additives comprising copolymers of ethylene and unsaturated carboxylic esters, preferably vinyl acetate, which are added to the fuels in amounts of from 0.01 to 0.5% by weight.
EP-A-0 764 198 discloses additives which improve the lubricating action of fuel oils and comprise polar nitrogen compounds based on alkylamines or alkyl ammonium salts containing alkyl radicals having 8 to 40 carbon atoms.
DE-A-15 94 417 discloses additives for improving the lubricating action of oleophilic liquids which comprise esters made from glycols and dicarboxylic acids having at least 11 carbon atoms.
EP-A-0 635 558 discloses diesel oils having sulfur contents of less than 0.2% by weight and aromatic contents of less than 30% by weight. These diesel oils contain, as additives, from 100 to 10,000 ppm of C1-C5-alkyl esters of unsaturated, straight-chain C12-C22-fatty acids originating from oil seed.
EP-A-0 074 208 discloses middle and heavy distillates containing, as additives, copolymers of ethylene and alkoxylated acrylates or ethylene and vinyl esters of saturated and unsaturated carboxylic acids.
The object of the present invention was to find additives which improve the lubricating action in middle distillates which have been substantially freed from sulfur and aromatic compounds. At the same time, these additives should also have a positive effect on the cold-flow properties of these middle distillates.
Surprisingly, it has been found that copolymers of ethylene and ethylenically unsaturated compounds carrying one or more hydroxyl groups provide the fuel oils to which they are added with the requisite properties.
The invention relates to copolymers of ethylene and at least one further olefinically unsaturated comonomer containing one or more hydroxyl groups.
The invention furthermore relates to fuel oils comprising middle distillates containing a maximum of 0.5% by weight of sulfur and at least one copolymer of ethylene and at least one further olefinically unsaturated comonomer containing one or more hydroxyl groups.
The olefinically unsaturated compounds which make up the further comonomer(s) are preferably vinyl esters, acrylates, methacrylates, alkyl vinyl ethers and/or alkenes carrying hydroxyalkyl, hydroxyalkenyl, hydroxycycloalkyl or hydroxyaryl radicals. These radicals contain at least one hydroxyl group, which can be in any desired position of the radical, but is preferably at the chain end (xcfx89-position).
The vinyl esters are preferably those of the formula 1
CH2xe2x95x90CHxe2x80x94OCOR1xe2x80x83xe2x80x83(1)
in which R1 is C1-C30-hydroxyalkyl, preferably C1-C2-hydroxyalkyl, especially C2-C6-hydroxyalkyl or the corresponding hydroxy oxalkyl. Suitable vinyl esters include 2-hydroxyethylvinyl esters, xcex1-hydroxypropylvinyl esters, 3-hydroxypropylvinyl esters and 4-hydroxybutylvinyl esters.
The acrylates are preferably those of the formula 2
CH2xe2x95x90CR2xe2x80x94COOR3xe2x80x83xe2x80x83(2)
in which R2 is hydrogen or methyl, and R3 is C1-C30-hydroxyalkyl, preferably C1-C12-hydroxyalkyl, especially C2-C6-hydroxyalkyl or the corresponding hydroxy oxalkyl. Suitable acrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glycerol monoacrylate.
The alkyl vinyl ethers are preferably compounds of the formula 3
CH2xe2x95x90CHxe2x80x94OR4xe2x80x83xe2x80x83(3)
in which R4 is C1-C30-hydroxyalkyl, preferably C1-C12-hydroxyalkyl, especially C2-C6-hydroxyalkyl or the corresponding hydroxy oxalkyl. Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol monovinyl ether.
The alkenes are preferably monounsaturated hydroxyhydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 carbon atoms, especially 5 to 12 carbon atoms. Suitable alkenes include dimethylvinylcarbinol (=2-methyl-3-buten-2-ol), allyloxypropanediol, 2-butene-1,4-diol, 1-buten-3-ol, 3-buten-1-ol, 2-buten-1-ol, 1-penten-3-ol, 1-penten-4-ol, 2-methyl-3-buten-1-ol, 1-hexen-3-ol, 5-hexen-1-ol and 7-octene-1,2-diol. In a further preferred embodiment the carbon chains of the alkenes contain oxygen atoms.
The invention furthermore relates to a process for improving the lubricating action of mineral oils and mineral oil distillates by adding the hydroxyl-containing copolymers designated in greater detail herein to the oils.
The molar proportion of hydroxy-functionalized comonomers in the copolymer is preferably from 0.5 to 15%, in particular from 1 to 12%. The OH number of the copolymers is preferably between 1 and 800 mg of KOH/g of polymer, in particular between 5 and 500 mg of KOH/g of polymer, especially between 10 and 300 mg of KOH/g of polymer.
The melt viscosities of the copolymers according to the invention at 140xc2x0 C. are preferably less than 10,000 mpas, in particular between 10 and 1000 mpas, especially between 15 and 500 mPas.
Besides ethylene, the copolymers according to the invention contain at least one comonomer containing hydroxyl groups. They may also contain further, for example one, two or three further, olefinically unsaturated comonomers. Examples of such olefinically unsaturated comonomers are vinyl esters, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, vinyl ethers and olefins. Particularly preferred vinyl esters are vinyl acetate, vinyl propionate and vinyl esters of neocarboxylic acids having 8, 9, 10, 11 or 12 carbon atoms. Particularly preferred acrylic and methacrylic esters are those with alcohols having 1 to 20 carbon atoms, in particular of methanol, ethanol, propanol, n-butanol, isobutanol and tert-butanol. Particularly preferred olefins are those having 3 to 10 carbon atoms, especially propene, isobutylene, diisobutylene, norbornene, 4-methyl-1-pentene and hexene. Particular preference is given to terpolymers of ethylene, a hydroxy-functionalized comonomer and either vinyl acetate or a vinyl ester of a neocarboxylic acid having 8 to 12 carbon atoms. If the copolymers contain a further comonomer, the molar proportion thereof is preferably up to 15%, in particular up to 12%.
The comonomers are copolymerized by known processes (cf. in this respect, for example, Ullmanns Encyclopxc3xa4die der Technischen Chemie [Ullmann""s Encyclopedia of Industrial Chemistry], 4th Edition, Vol. 19, pages 169 to 178). Suitable processes are polymerization in solution, in suspension or in the gas phase and high-pressure bulk polymerization. Preference is given to high-pressure bulk polymerization, which is carried out at pressures of from 50 to 400 MPa, preferably from 100 to 300 MPa, and at temperatures of from 50 to 350xc2x0 C., preferably from 100 to 300xc2x0 C. The reaction of the comonomers is started by initiators which form free radicals (free-radical chain initiators). This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds, such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis(2-ethylhexyl) peroxydicarbonate, t-butyl permaleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di(t-butyl) peroxide, 2,2xe2x80x2-azobis(2-methylpropanonitrile) and 2,2xe2x80x2-azobis(2-methylbutyronitrile). The initiators are employed individually or as a mixture of two or more substances in amounts of from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the comonomer mixture.
The desired melt viscosity of the copolymers is set for a given composition of the comonomer mixture by varying the reaction parameters pressure and temperature and if desired by adding moderators. Moderators which have proven successful are hydrogen, saturated and unsaturated hydrocarbons, for example propane, aldehydes, for example propionaldehyde, n-butyraldehyde and isobutyraldehyde, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohols, for example butanol. Depending on the desired viscosity, the moderators are used in amounts of up to 20% by weight, preferably from 0.05 to 10% by weight, based on the comonomer mixture.
High-pressure bulk polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors. Tubular reactors have proven particularly successful. Solvents, such as aliphatic hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be present in the reaction mixture, although the solvent-free procedure has proven particularly successful. In a preferred way of carrying out the polymerization, the mixture of the comonomers, the initiator and, if used, the moderator is fed to a tubular reactor via the reactor inlet and via one or more side branches; the comonomer streams can have different compositions (EP-B-0 271 738).
The novel improvement in the lubricating action of oils can likewise be effected by copolymers containing structural units derived from ethylene and vinyl alcohol. Copolymers of this type can be prepared by partially or fully hydrolyzing a copolymer containing structural units derived from ethylene and vinyl acetate.
Likewise, copolymers derived from ethylene and monomers carrying glycidyl radicals, such as, for example, glycidyl (meth)acrylate or glycidyl allyl ether, can also be used in accordance with the invention after hydrolysis using water, alcohols, such as methanol or glycol, or amines, such as, for example, ammonia, methylamine, ethanolamine and diethanolamine.
The lubricating action of oils can furthermore be improved in the manner according to the invention by admixing them with ethylene copolymers containing alkoxylated acid groups. Examples of ethylene copolymers which are suitable for this purpose are those containing acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride. In order to prepare an additive which improves the lubricating action of oils, these copolymers containing acid groups are alkoxylated on the acid groups using C1- to C10-alkylene oxides. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxides. The alkoxylation is preferably carried out using from 0.5 to 10 mol, in particular from 1 to 5 mol, especially from 1 to 2 mol, of alkylene oxide per mole of acid groups.
The copolymers according to the invention are added to mineral oils or mineral oil distillates in the form of solutions or dispersions comprising from 10 to 90% by weight, preferably from 20 to 80%, of the polymers. Suitable solvents or dispersion media are aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures, such as solvent naphtha, (copyright)Shellsol AB, (copyright)Solvesso 150, (copyright)Solvesso 200, (copyright)Exxsol-, (copyright)ISOPAR and Shellsol D products. Mineral oils and mineral oil distillates whose lubricating and/or cold-flow properties have been improved by the copolymers contain from 0.001 to 2% by weight, preferably from 0.005 to 0.5% by weight, of copolymer, based on the distillate.
The copolymers according to the invention may furthermore be used in the form of mixtures consisting of copolymers of the type claimed, but of different qualitative and/or quantitative composition and/or of different viscosity (measured at 140xc2x0 C.). The mixing ratio (in parts by weight) of the copolymers can be varied over a broad range and can be, for example from 20:1 to 1:20, preferably from 10:1 to 1:10. In this way, the additives can be matched specifically to individual requirements.
In order to prepare additive packages for specific problem solutions, the copolymers according to the invention can also be employed together with one or more oil-soluble co-additives. Examples of such co-additives are polar compounds which effect paraffin dispersal (paraffin dispersants), comb polymers and oil-soluble amphiphilic compounds.
For use as flow improvers and/or lubricity additives, the copolymers according to the invention can furthermore be employed in the form of a mixture with paraffin dispersants. These additives reduce the size of the paraffin crystals and prevent the paraffin particles from settling out, but instead ensure that they remain colloidally dispersed with significantly reduced sedimentation effort. Furthermore, they reinforce the lubricating action of the copolymers according to the invention. Paraffin dispersants which have proven successful are oil-soluble polar compounds containing ionic or polar groups, for example amine salts and/or amides, which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or anhydrides thereof (cf. U.S. Pat. No. 4,211,534). Other paraffin dispersants are copolymers of maleic anhydride and xcex1,xcex2-unsaturated compounds, which, if desired, can be reacted with primary monoalkylamines and/or aliphatic alcohols (cf. EP 0 154 177), the products of the reaction of alkenylspirobislactones with amines (cf. EP 0 413 279 B1) and, according to EP 0 606 055 A2, products of the reaction of terpolymers based on xcex1,xcex2-unsaturated dicarboxylic anhydrides, xcex1,xcex2-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. Alkylphenol-aldehyde resins are also suitable as paraffin dispersants.
Finally, in a further proven variant of the invention, the copolymers according to the invention can be used together with comb polymers. This is taken to mean polymers in which hydrocarbon radicals having at least 8 carbon atoms, in particular at least 10 carbon atoms, are bonded to a polymer backbone. These are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymersxe2x80x94Structure and Properties; N. A. Platxc3xa9 and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate-vinyl acetate copolymers (cf. EP 0 153 176 Al), copolymers of a C6- to C24-xcex1-olefin and an Nxe2x80x94C6- to C22-alkylmaleimide (cf. EP 0 320 766), furthermore esterified olefin-maleic anhydride copolymers, polymers and copolymers of xcex1-olefins and esterified copolymers of styrene and maleic anhydride.
Comb polymers can be described, for example, by the formula 
in which
A is Rxe2x80x2, COORxe2x80x2, OCORxe2x80x2, Rxe2x80x3xe2x80x94COORxe2x80x2 or ORxe2x80x2;
D is H, CH3, A or Rxe2x80x3;
E is H or A;
G is H, Rxe2x80x3, Rxe2x80x3xe2x80x94COORxe2x80x2, an aryl radical or a heterocyclic radical;
M is H, COORxe2x80x3, OCORxe2x80x3, ORxe2x80x3 or COOH;
N is H, Rxe2x80x3, COORxe2x80x3, OCOR, COOH or an aryl radical;
Rxe2x80x2 is a hydrocarbon chain having 8-50 carbon atoms;
Rxe2x80x3 is a hydrocarbon chain having 1 to 10 carbon atoms;
m is a number between 0.4 and 1.0; and
n is a number between 0 and 0.6.
The mixing (in parts by weight) of the terpolymers prepared in accordance with the invention with paraffin dispersants or comb polymers is in each case from 1:10 to 20:1, preferably from 1:1 to 10:1.
In order to optimize the lubricating action, the copolymers according to the invention can be employed in the form of a mixture with further lubricity additives. Lubricity additives which have proven successful are preferably oil-soluble amphiphilic compounds, such as, for example, fatty alcohols, fatty acids and dimeric fatty acids, and esters and partial esters thereof with glycols (as described in DE-A-15 94 417), polyols, such as glycerol (as described in EP-A-0 680 506, EP-A-0 739 970) or hydroxylamines (as described in EP-A-0 764 198).
The additives according to the invention are suitable for improving the lubricating and cold-flow properties of animal, vegetable or mineral oils and of alkanol-containing fuels. In addition, they retard or prevent sedimentation of precipitated paraffin crystals. They are particularly suitable for use in middle distillates. The term middle distillates is taken to mean, in particular, mineral oils boiling in the range from 120 to 450xc2x0 C., and obtained by distillation of crude oil. Examples include kerosene, jet fuel, diesel and heating oil. The copolymers according to the invention are preferably used in middle distillates containing 0.5% by weight or less of sulfur, in particular less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur. These are generally middle distillates which have been hydrotreated and therefore contain only small proportions of polyaromatic and polar compounds which give them a natural lubricating action. The copolymers according to the invention are furthermore preferably used in middle distillates having 95% distillation points of below 370xc2x0 C., in particular below 350xc2x0 C. and in special cases below 330xc2x0 C.
The polymers can be used alone or together with other additives, for example with other pour point depressants or dewaxing auxiliaries, with corrosion inhibitors, antioxidants, detergent additives, cetane number improvers, sludge inhibitors, dehazers and additives for lowering the cloud point.